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a
b
O
O
H
H
OH
N
N
N
O
H
O
O
O
Precursor (14)
O
N
H
N
N
OH
H
O
O
Hydrogelator (15)
Fig. 9 Intracellular cleavage of an esterase substrate ( 14 ) by an endogenous esterase to the hydro-
gelator ( 15 ) and corresponding formation of supramolecular assembly within the cells. Reproduced
with permission from [ 75 ] Copyright Wiley-VCH Verlag GmbH & Co. KGaA
7
Conclusion and Outlook
A number of dynamic supramolecular polymers control vital functions in biology.
These are tightly regulated by highly selective and spatially confined catalytic mech-
anisms whereby non-assembling precursors are catalytically activated to produce
self-assembling components.
Over the past 5 years, a number of researchers have started to explore and mimic
these approaches in the laboratory. Enzyme-assisted formation of supramolecular
polymers has several unique features. These include selectivity, confinement and
catalytic amplification, which allow for superior control as observed in biologi-
cal systems. These systems are finding applications in areas where supramolecular
function is directly dictated by molecular order, for example in designed biomateri-
als for 3D cell culture, templating, drug delivery, biosensing, and intracellular poly-
merisations to control cell fate. Overall, biocatalytic production of supramolecular
polymers provides a powerful new paradigm in stimuli-responsive nanomaterials.
References
1. Lehn JM (1995) Supramolecular chemistry - concepts and perspectives. VCH Weinheim
2. Lehn JM (2002) Supramolecular polymer chemistry - scope and perspectives. Polym Int
51:825-839
3. Mart RJ, Osborne RD, Stevens MM, Ulijn RV (2006) Peptide-based stimuli-responsive bio-
materials. Soft Matter 2:822-835
4. Jayawarna
V,
Ali
M,
Jowitt
TA,
Miller
AF,
Saiani
A,
Gough
JE,
Ulijn
RV
(2006)
Nanostructured
hydrogels
for
three-dimensional
cell
culture
through
self-assembly
of
fluorenylmethoxycarbonyl-dipeptides. Adv Mater 18:611-614
 
 
 
 
 
 
 
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